JPS60115533A - Oligomerization process - Google Patents

Abstract

PURPOSE:To carry out the oligomerization of an alkenyl- or alkylidenenorbornene, economically, by using a catalyst comprising a combination of an organic alkali metal compound with a specific complexing agent such as a substituted polymethylenediamine, substituted polyethylene-polyamine, etc. CONSTITUTION:The dimer of the compound of formula III or formula IV (R1-R4 are H or CH3) useful especially as a reactive plasticizer, etc. is produced economically by oligomerizing the compound preferably at 95-170 deg.C, in the presence of a binary catalyst comprising a combination of (A) an organic alkali metal compound (the alkali metal is Na and/or K) and (B) one or more complexing agents selected from (i) the compound of formula I (n is integer of >=2; R1-R4 are alkyl, cycloalkyl, aryl or aralkyl), (ii) the compound of formula IIand (iii) triethylenediamine. High dimerization activity can be attained by using 0.1-5mol-equivalent, especially 0.5-2mol-equivalent of the complexing agent based on the organic alkali metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for oligomerizing alkenyl or alkylidene norbornenes.

Alkylidenenorbornene used as one of the starting materials in the present invention is represented by the following formula (I).

Here, R1 to R4 are hydrogen atoms or methyl groups.

Specific compounds of the alkylidene norbornene mentioned above include ethylidene norbornene, propylidene norbornene, inpropylidene norbornene, and ethylidene methyl norbornene.

Another starting material is alkenylnorbornene of the following formula (II).

Here, R1 to R4 are hydrogen atoms or methyl groups.

Specific examples of the alkenylnorbornene mentioned above include vinylnorbornene, propenylnorbornene, isopropenylnorbornene, and vinylmethylnorbornene.

When the above-mentioned alkenylnorbornene is treated with the two-way catalyst of the present invention described below, it is isomerized to alkylidene norbornene of formula (I), followed by oligomerization. Therefore, the above-mentioned alkenylnorbornene can also be used as a starting material.

Note that norbornene of formula (I) and formula (II) also refers to
There are stereoisomers such as cis form and trans form, and any of them can be used.

The catalyst of the present invention is a two-way catalyst in which an organic alkali metal compound is combined with a complexing agent. The organic alkali metal compound in the present invention is a compound represented by the general formula R-Me, and Me
is sodium or potassium, and R represents an alkyl group such as methyl, ethyl, propyl, butyl, or pentyl, an alkenyl group such as allyl or metaallyl, a cycloalkyl group such as cyclohexyl, or an aryl or aralkyl group such as phenyl or benzyl. .

Also included as organic alkali metal compounds are complexes (charge transfer complexes) of polycyclic aromatic compounds such as anthracene and sodium or potassium. Furthermore, a mixture of two or more of these can also be used. These organic alkali metal compounds may be prepared within the dimerization reaction system, or may be prepared separately outside the dimerization reaction system.

In the present invention, the complexing agent combined with the organic alkali metal compound is one or a mixture of two or more of the following complexing agents.

That is, (a) where n is an integer of 2 or more, and R1, R2, R3 and R4 are alkyl, cycloalkyl and aryl groups, such as tetramethylethylenediamino, tetramethylethylenediamine, tetramethylpropylenediamine, etc. and tetra-substituted polymethylene diamines.

(b) Here, n is an integer of 2 or more, and R1, R2, R3 and R4 are alkyl, cycloalkyl and aryl groups, and represent a substituted polyethylene polyamine such as pentamethyldiethylenetriamine.

(c) Triethylenediamine When these complexing agents act on an organic alkali metal compound, a significant change in hue occurs, and the organic alkali metal compound that is insoluble in hydrocarbons becomes solubilized, suggesting the formation of a complex.

The amount of complexing agent combined with the organic alkali metal compound is
Although not particularly limited, the dimerization activity becomes remarkable when a complexing agent is usually used in an amount of 0.1 to 5 molar equivalents, preferably 0.5 to 2 molar equivalents, relative to the organic alkali metal compound. When the amount of complexing agent is small, effective complex formation is small;
On the other hand, it is not economical to use an excessive amount of complexing agent, and it is also disadvantageous as it may reduce the catalytic activity.

The amount of the organic alkali metal compound used in the present invention is not particularly limited, but is usually 0.1 to 100 mmol per mol of alkenyl or alkylidene norbornene.
Preferably it is in the range of 0.5 to 50 mmol.

The dimerization of the present invention can be carried out without a solvent, or it is also possible to use a solvent inert to the reaction, such as an aliphatic hydrocarbon or an aromatic hydrocarbon.

The reaction temperature for oligomerization is 20-220°C, preferably 95-170°C.

The reaction time is not particularly limited as long as it is long enough to complete the dimerization reaction, but is usually 30 minutes to 24 hours.

Further, this oligomerization can be carried out under normal pressure or increased pressure, and can also be carried out by a batch method, a semi-batch method, or a continuous method.

As described above, an oligomer can be obtained by reacting norbornene of formula (I) or formula (II) with a binary catalyst of an organic alkali metal compound and a complexing agent. According to the method of the present invention, dimers are mainly produced, but up to pentamers can be produced by selecting reaction conditions.

In the oligomerization method of the present invention, the reaction proceeds without ring-opening of the norbornene ring, that is, the unsaturated side chain of norbornene becomes an active site, and the active site is added to the endocyclic unsaturated bond of norbornene. The reaction proceeds accordingly.

The oligomer, especially the dimer, obtained by the present invention is a liquid substance with high density and low pour point, so it can be used as a reactive plasticizer as it is, or by hydrogenation as appropriate. It can be used in high-density liquid fuels, plasticizers, and other lubricating oils.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 In a 2 liter autoclave purged with nitrogen, 5-vinylnorbornene-2 (4 mol), sodium phenyl prepared by reaction of chlorobenzene with a sodium dispersion in benzene (0.08 mol, 200 ml of benzene) and tetra After adding methylethylenediamine (0.16 mol), the mixture was reacted at 120°C for 6 hours.

After the reaction is completed, the reaction solution is washed with water, dried, and distilled under reduced pressure to obtain an oligomer with a boiling point of 135 to 156°C/2 mmHg in a yield of 3.
Obtained at 5%.

(Oligomer physical properties) Boiling point 135-156℃/2mmHg Specific gravity 0.981 Pour point -40℃ (Analysis) According to the mass spectrum, the molecular weight of the oligomer is 240
It was hot.

Also, from the infrared spectrum, 800 cm-1 and 16
Absorption of a trisubstituted double bond was observed at 90 cm −1 , and absorption of a cis-type double bond was also observed.

According to proton NMR (solvent: CCl4), the proton ratios are as follows.

Proton ratio 0.5-1 ppm 1 1-3.5 ppm 19 4.5-5.8 ppm 2 5.8-6.3 ppm 2 Total 24 From the analysis results, it was found that oligomers are mainly dimers. .

Furthermore, the structure of the dimer was such that an unsaturated bond in the side chain was added to an endocyclic unsaturated bond.

Example 2 An oligomer with a boiling point of 136 to 155°C/2 mmHg was obtained by reacting in the same manner as in Example 1, except that 5-ethylidenenorbornene-2 was replaced with 5-vinylnorbornene-2 (yield: 15%). ).

When the physical properties, mass spectrum, 1R spectrum and NMR spectrum of this oligomer were measured, Example 1
It showed almost the same value as the oligomer.

Claims (1)

[Claims] (1) an organic alkali metal compound (wherein n is an integer greater than or equal to 2, R1, R2, R3 and R
4 represents an alkyl, cycloalkyl, aryl and aralkyl group; 1. A method for oligomerizing alkenyl or alkylidene norbornene, which comprises using a catalyst in combination with a complexing agent selected from the group consisting of a substituted polyethylene polyamine (representing a group) and (c) triethylenediamine.